Stereoselective formation of boron-stereogenic organoboron derivatives.

Four-coordinate organoboron derivatives present interesting chemical, physical, biological, electronical, and optical properties. Given the increasing demand for the synthesis of smart functional materials based on chiral organoboron compounds, the exploration of stereoselective synthesis of boron-stereogenic organo-derivatives is highly desirable. However, the stereoselective construction of organoboron compounds stereogenic at boron has been far less studied than other elements of the main group due to configurational stability concerns. Nowadays, these species are no longer elusive and configurationally stable compounds have been highlighted. The idea is to show the potential of the stereoselective building of the four-coordinate boron centre and encourage future endeavors and developments in the field.

Highly diastereoselective preparation of chiral NHC-boranes stereogenic at the boron atom.

Stereogenic main group elements are clearly generating interest in the enantioselective catalysis field. Surprisingly, while chiral organoboron reagents are very useful in stereoselective transformations, few scaffolds stereogenic at boron and configurationally stable have been reported to date. Herein, we describe an original library of chiral NHC-boranes, stereogenic at the boron atom, that has been prepared in only a few steps and in good yields (up to 93%). Key steps involve a chlorination/arylation sequence in the presence of simple Grignard reagents from bicyclic NHC-boranes. The high and unprecedented diastereoselectivity observed during the second step (up to 99 : 1 dr) has been rationalized through a plausible SRN1 mechanism thanks to EPR observations and DFT calculations.

Aziridination of Cyclic Nitrones Targeting Constrained Iminosugars.

Rare C-7-substituted aziridinyl iminosugars can be synthesized through a short reaction sequence involving 1,3-cycloaddition of cyclic nitrones with alkynes and a Baldwin rearrangement of isoxazolines into bicyclic 2-acylaziridines. The method is efficient and completely diastereoselective, producing stable aziridinyl iminosugars in high yields.

In Situ Determination of Fructose Isomer Concentrations in Wine Using (13)C Quantitative Nuclear Magnetic Resonance Spectroscopy.

A practical method for simultaneously quantifying fructose and ethanol contents in wines using (13)C quantitative nuclear magnetic resonance (qNMR) spectroscopy is reported. Less than 0.6 mL of wine is needed, and the method leaves an unmodified sample available for subsequent testing or additional analyses. The relative ratios of the five known fructose isomers in ethanolic solutions at different pH and their variations with the temperature are also reported. The data are correlated with the sweetness of wines. The technique was applied to commercially available wines, and the results are compared to other methods. Sugar levels above 0.6 g/L can also be measured. A simple adaptation of the method permits measurement of different carbohydrates using integration of single peaks for each compound, in combination with an external reference (13)C qNMR spectrum of a sample with a known concentration. The method can be applied at all stages of wine production, including grape must, during fermentation, and before and after bottling.